Water-soluble reactive mono- and di-azo dyes

ABSTRACT

Water-soluble monoazo and disazo dyes 
 
The present invention relates to dyes of the general formula (I)  
                 
where  
     X 1  is a radical —CH 2 CH 2 Z or —CH═CH 2 , Z being analkali-eliminable group,  
     X 2  is alkyl, alkoxy, halogen, COOM or SO 3 M,  
     X 3  is a heterocyclic reactive group of the general formula (IIa) or (IIb)  
                 
 
or a reactive group of the formula (IIc), (IId) or (IIe)  
                 
 
     the stated variables being as defined in claim  1,  to processes for preparing them and to their use for dyeing and printing hydroxyl-containing and/or carboxamido-containing material.

The present invention is situated within the field of fiber-reactive dyes. EP-A 785 237 discloses reactive dyes comprising the structural element

The present invention now provides dyes of the general formula (I)

where

-   m is 1 or 2, -   n is 0 or 1 -   q is 0, 1, 2 or 3 and -   p is 0, 1 or 2, -   r is 0, 1 or 2, and -   p+r is 1 or 2 and -   X₁ is a radical —CH₂CH₂Z or —CH═CH₂, Z being an alkali-eliminable     group, -   M is hydrogen, ammonium, an alkali metal or the equivalent of an     alkaline earth metal, -   X₂ is alkyl, alkoxy, halogen, COOM or SO₃M, -   L is a direct bond or alkylene, -   L′ is a direct bond or a group of the formula -   X₃ is a heterocyclic reactive group of the general formula (IIa) or     (IIb)     or a reactive group of the formula (IIc), (IId) or (IIe)     where -   X₄ to X₆ independently are hydrogen or halogen, with the proviso     that at least one radical X₄ to X₆ is halogen, -   X₇ is halogen or X₈, and -   X₈ is a substituent of the general formula (III)     where -   R₁ is hydrogen, alkyl or aryl, -   B is alkylene, oxygen-interrupted alkylene, arylene or arylalkylene,     and -   R₂ is a radical SO₃M, SO₂—CH₂CH₂Z or SO₂—CH═CH₂, in which Z is as     defined above -   and the ring labeled A is either absent or present.

In the compound of the general formula (I) an alkali metal M can be in particular lithium, sodium or potassium, while calcium is a particularly suitable alkaline earth metal. Preferably M is hydrogen or sodium.

-   Halogen X₂, X₄ to X₆, and X₇ is in particular fluorine or chlorine. -   Alkyl R₁ or X₂ is preferably C₁-C₈ alkyl and more preferably C₁-C₄     alkyl. Examples of such alkyl groups are methyl, ethyl, n-propyl,     isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Especially     preferred alkyl groups are methyl and ethyl. Similar comments apply     to alkoxy R₁ or X₂. Especially preferred alkoxy groups, therefore,     are methoxy and ethoxy. -   Aryl R₁ is in particular phenyl, which may also be substituted one     or more times by, for example, C₁-C₄ alkyl, C₁-C₄ alkoxy, chloro,     fluoro or the SO₃H group. Alkylene B or L is preferably C₁-C₈     alkylene and more preferably C₁-C₄ alkylene. Examples of such     alkylene groups are methylene, ethylene, n-propylene, isopropylene,     and butylene. Oxygen-interrupted alkylene is in     particular—(CH₂)_(u)—O—(CH₂)_(v)-, in which u and v independently     are numbers from 1 to 3. -   Arylene B is in particular phenylene and naphthylene, preference     being given to meta- and para-phenylene. -   Arylalkylene B is preferably a group of the general formula (IVa) or     (IVb)     where s is a number from 1 to 4 and the free bond on the aromatic     nucleus may be attached either to N or to R₂. -   Alkali-eliminable radicals Z, i.e., radicals Z which can be     eliminated under dyeing conditions, include for example chloro,     bromo, sulfato, thiosulfato, phosphato, C₂-C₅ alkanoyloxy such as     acetyloxy, for example, benzoyloxy, sulfobenzoyloxy or     p-tolylsulfonyloxy, preference being given to sulfato. -   The groups, “sulfato”, “thiosulfato” and “phosphato” include both     the acid form and the salt form. Accordingly, thiosulfato groups     have the general formula —S—SO₃M, phosphato groups the general     formula —OPO₃M₂ and sulfato groups have the general formula —OSO₃M,     in which M is as defined above.

Preferred compounds of the general formula (I) meet the condition p+r=1, while paricularly preferred compounds of the general formula (I) meet the condition p+r=2. If m=1 then preferably p+r=1.

X₂ is preferably C₁-C₄ alkyl, C₁-C₄ alkoxy or SO₃M and more preferably methyl, ethyl, methoxy, ethoxy or SO₃M, in which M is hydrogen or sodium.

-   L and L′ are preferably each a direct bond. -   X₃ is preferably a group of the formula     where -   Hal′ is chloro or bromo, -   R₁′ is hydrogen, methyl, ethyl or phenyl, -   B′ is ethylene, propylene or —CH₂CH₂—O—CH₂CH₂- and -   R₂′ is —SO₂CH₂CH₂OSO₃M or —SO₂CH═CH₂.

If r is 2 then the radicals X₃ may have identical or different meanings. Similarly, the radicals X₂ may have identical or different meanings if q is 2 or 3 and the radicals X₁ may have identical or different meanings if p is 2.

Particularly preferred dyes of the general formula (I) correspond to the general formula (Ia)

where X₁ to X₃, A, L, L′, M, m, r, p and q are as defined above.

Particularly preferred dyes of the general formula (I) correspond, moreover, to the general formula (Ib)

where X₁ to X₃, A, L, L′, M, r, p and q are as defined above.

Particularly preferred dyes of the general formula (I) correspond, furthermore, to the general formula (Ic)

where M, X₂ and q are as defined above and V is X₃-NH-L- or X₁—O₂S-L′-, where X₁, X₃, A, L and L′ are as defined above.

Especially preferred dyes of the general formula (I) correspond to the following general formulae (Id) to (Iq)

where in each case

-   M is hydrogen or sodium and -   X₂′ is hydrogen, methyl, ethyl, methoxy, ethoxy, COOM or SO₃M and -   U is —SO₂CH₂CH₂OSO₃M, —SO₂CH═CH₂ or —NH-U′, in which M is hydrogen     or sodium and U′ is one of the formulae     where -   Hal′ is chloro or fluoro, -   R₁′ is hydrogen, methyl, ethyl or phenyl, -   B′ is ethylene, propylene or —CH₂CH₂—O—CH₂CH₂- and -   R₂′ is —SO₂CH₂CH₂OSO₃M or —SO₂CH═CH₂.

The dyes of the general formula (I) according to the invention are generally in the form of preparations in solid or liquid (dissolved) form. In solid form they generally include the electrolyte salts which are customary for water-soluble and especially fiber-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and may further include the assistants customary in commercial dyes, such as buffer substances with the capacity to set a pH in aqueous solution of between 3 and 7, such as sodium acetate, sodium borate, sodium hydrogen carbonate, sodium dihydrogen phosphate, sodium tricitrate, and disodium hydrogen phosphate, small amounts of siccatives or, if they are in liquid, aqueous solution (including the thickener content customary in the case of printing pastes), substances which ensure the durability of said preparations, such as mold preventatives, for example. The dyes of the general formula (I) according to the invention are preferably in the form of dye powders or dye granules containing from 10 to 80% by weight, based on the powder or granules, of an electrolyte salt, also referred to as a standardizer. Granules have grain sizes in particular of from 50 to 500 μm. These solid preparations may further comprise the abovementioned buffer substances in a total amount of up to 10% by weight, based on the preparation. Where the dyes are in aqueous solution, the total dye content of such aqueous solutions is up to about 50% by weight, such as between 5 and 50% by weight, for example, with the electrolyte salt content of these aqueous solutions being preferably below 10% by weight, based on the aqueous solution. The aqueous solutions (liquid preparations) may comprise the abovementioned buffer substances, in general, in an amount of up to 10% by weight, preferably up to 2% by weight.

Dyes of the general formula (I) where p≠0 and/or those containing a group of the formula (IIb) in which X₈ is a group of the formula (III), while having the same chromophore, may possess a different structure in respect of the fiber-reactive group SO₂X₁ and/or R₂. In particular, with the same chromophore, SO₂X₁ and R₂ may on the one hand be —SO₂CH═CH₂ and on the other —SO₂CH₂CH₂Z, with particular preference β-sulfatoethylsulfonyl. The fraction of the dye in vinylsulfonyl form may be up to about 30 mol %, based on the respective dye chromophore. The molar ratio between the vinylsulfonyl dye fraction and the β-ethyl-substituted dye fraction is preferably between 5:95 and 30:70.

The dyes of the general formula I according to the invention may be prepared, for example, by diazotizing an aromatic amine of the general formula (V)

where p, q, r, A, L, X₁, X₂ and X₃ are as defined above and coupling the diazonium compound with a compound of the general formula (VI)

Using one equivalent of compound of the general formula (V) in this preparation process per equivalent of compound of the general formula (VI) produces dyes of the general formula (I) according to the invention in which m is 1. Alternatively, using two equivalents of compound of the general formula (V) per equivalent of compound of the general formula (VI) produces dyes of the general formula (I) according to the invention in which m is 2.

-   Where the intention is to prepare a compound of the general     formula (I) according to the invention in which m is 2, the     condition p+r=1 or 2 is not met in the aromatic compounds of the     general formula (V). Instead, p and r are to be chosen such that the     resulting compound of the general formula (I) according to the     invention meets the condition p+r=1 or 2.

In one preferred embodiment of the preparation process according to the invention first one equivalent of aromatic amine of the general formula (V) is diazotized and the diazonium compound is coupled with one equivalent of a compound of the general formula (VIa)

where M is as defined above in the pH range between 0 and 6, preferably between 1 and 4. The resultant monoazo dyes correspond to the general formula (Ir)

where p, q, r, A, L, X₁, X₂, X₃ and M are as defined above.

-   The dyes of the general formula (Ir) dye cotton in golden yellow to     reddish yellow shades with good all-round fastness properties.

The dyes of the general formula (Ir) can then if desired be reacted with a second equivalent of the aromatic amine of the general formula (V), diazotized beforehand by known methods, to give disazo dyes of the general formula (Ia) or (Ib).

In the preparation according to the invention of compounds of the general formula (I) in which m is 2 the two equivalents of aromatic amine may be the same or different in respect of the variables p, q, r, L, L′, X₁, X₂ and X₃.

If the two equivalents of aromatic amine are the same in respect of the variables p, q, r, L, L′, X₁, X₂ and X₃ then it is particularly preferred to perform the reaction in a one-pot process (“one-pot coupling”). In this case two equivalents of the aromatic amine of the general formula (V) are diazotized and the diazonium compound is coupled with one equivalent of the compound of the general formula (VI).

-   The compounds of the general formula (I) according to the invention     that are obtained by one-pot coupling are identical with the     compounds obtained by “serial coupling”: that is, by twofold     successive coupled attachment of in each case one equivalent of     aromatic amine of the general formula (V) of the same chemical     structure.

Dyes of the general formula (I) according to the invention in which m is 2 and p+r=1 may be prepared by diazotizing an aromatic amine of the general formula (V) in which p+r=0 and reacting the diazonium compound with a compound of the general formula (VI) to give a compound of the general formula (VII)

where q, n, A, X₂ and M are as defined above. Then, in a second step, an aromatic amine of the general formula (V) in which p+r=1 is diazotized and the diazonium compound is coupled further with the compound of the general formula (VII) to give the disazo dye according to the invention.

-   Conversely it is also possible, of course, first to diazotize an     aromatic amine of the general formula (V) in which p+r=1 and to     couple the diazonium compound with a compound of the general     formula (VI) to give dyes of the general formula (Is) according to     the invention     where n, p, q, r, A, L, X₁, X₂, X₃ and M are as defined above and in     which p+r=1. Then, in the second step, an aromatic amine of the     general formula (V) in which p+r=0 is diazotized and the diazonium     compound is subjected to further coupling to give the disazo dye     according to the invention. In both cases monofunctional disazo     reactive dyes are obtained which, given an appropriate choice of     first and second diazo component, are isomeric with one another. -   Preferred aromatic amines of the general formula (V) in which p+r=0     are aniline derivatives or naphthylamine derivatives, but especially     their sulfonic acids. -   Examples that may be mentioned include aniline-2-sulfonic acid,     aniline-3-sulfonic acid, aniline-4-sulfonic acid,     4-methylaniline-2-sulfonic acid, 4-methylaniline-3-sulfonic acid,     4-methylaniline-2,5-disulfonic acid, 4-methoxyaniline-2-sulfonic     acid, 4-methoxyaniline-2,5-disulfonic acid,     2-chloroaniline-5-sulfonic acid, 2-chloroaniline-4-sulfonic acid,     2-methoxy-5-methylaniline-4-sulfonic acid,     2,5-dimethoxyaniline-4-sulfonic acid, aniline-2,4-disulfonic acid,     aniline-2,5-disulfonic acid, 2-methoxyaniline-5-sulfonic acid,     1-aminonaphthalene-2-sulfonic acid, 1-aminonaphthalene-3-sulfonic     acid, 1-aminonaphthalene-4-sulfonic acid,     1-aminonaphthalene-5-sulfonic acid, 1-aminonaphthalene-6-sulfonic     acid, 1-aminonaphthalene-7-sulfonic acid,     1-aminonaphthalene-8-sulfonic acid,     1-aminonaphthalene-3,6-disulfonic acid,     1-aminonaphthalene-3,7-disulfonic acid,     1-aminonaphthalene-4,8-disulfonic acid,     2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-5-sulfonic     acid, 2-aminonaphthalene-6-sulfonic acid,     2-aminonaphthalene-7-sulfonic acid, 2-aminonaphthalene-8-sulfonic     acid, 2-aminonaphthalene-1,5-disulfonic acid,     2-aminonaphthalene-4,8-disulfonic acid,     2-aminonaphthalene-5,7-disulfonic acid,     2-aminonaphthalene-6,8-disulfonic acid,     2-aminonaphthalene-3,6-disulfonic acid,     2-aminonaphthalene-1,5,7-trisulfonic acid and     2-aminonaphthalene-3,6,8-trisulfonic acid. -   Preferred aromatic amines of the general formula (V) in which p+r≠0     correspond to the aforementioned compounds but additionally carry     the corresponding number of substituents -L′—SO₂X₁ and/or -L—NH-X₃.

The diazotization and coupling reactions needed to prepare the dyes of the general formula (I) are known per se to the skilled worker and can be performed in conventional manner as described thoroughly in the relevant literature. In the case of the preparation processes-indicated the dyes of the general formula (I) according to the invention are obtained as solutions or suspensions and can be isolated by salting out, for example. The dyes can also be spray dried, although evaporative concentration of the solution or suspension is a further possibility.

The aromatic amines of the general formula (V) are known per se and can be prepared by methods familiar to the skilled worker.

-   The compounds of the general formula (VI) have in some instances     likewise been described (for example,     3-sulfomethylaminoaniline-6-sulfonic acid in JP 60 243157 and JP 61     57650). They may be prepared, for example, by reacting compounds of     the general formula (VIII)     in which n is 0 or 1 with formaldehyde bisulfite of the formula (IX)     where M is as defined above. For this reaction it is customary to     add formaldehyde bisulfite to a solution of compound of the general     formula (VIII) at a pH of from 3 to 9 and to carry out condensation     at a reaction temperature of from 30 to 80° C.

The reactive dyes of the general formula (I) according to the invention possess useful application properties. They are used for dying and printing hydroxyl—and/or carboxamido-containing materials, in the form for example of sheetlike structures, such as paper and leather, or of films, of polyamide, for example, or in bulk, as for example polyamide and polyurethane, but especially in the form of fibers of the materials mentioned. Preferably they are used for dyeing and printing cellulosic fiber materials of any kind. They are additionally suitable for dyeing or printing hydroxyl-containing fibers present in blend fabrics; for example, blends of cotton with polyester fibers or polyamide fibers. It is also possible to use them to print textiles or paper by the inkjet process.

The present invention accordingly also provides for the use of the reactive dyes of the general formula (I) according to the invention for dyeing or printing the materials mentioned and, respectively, provides methods of dyeing or printing such materials in a conventional manner using as colorants one or more reactive dyes of the general formula (I) according to the invention.

Advantageously the as-synthesized solutions of the reactives dyes of the general formula (I) according to the invention may be used directly as a liquid preparation for dyeing, where appropriate following addition of a buffer substance and similarly where appropriate following concentration or dilution.

The materials mentioned are used preferably in the form of fiber materials, particularly in the form of textile fibers, such as wovens or yarns, as in the form of hanks or wound packages.

-   Hydroxyl-containing materials are those of natural or synthetic     origin, examples being cellulose fiber materials or regenerated     products thereof and polyvinyl alcohols. Cellulose fiber materials     are preferably cotton but also include other plant fibers, such as     linen, hemp, jute, and ramie fibers. Regenerated cellulose fibers     are, for example, staple viscose and filament viscose.

Carboxamido-containing materials are, for example, synthetic and natural polyamides and polyurethanes, particularly in fiber form, examples being wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-1 1 and nylon-4.

The reactive dyes of the general formula (I) according to the invention may be applied to and fixed on the substrates mentioned, particularly the fiber materials mentioned, by the application techniques that are known for water-soluble dyes and in particular by the techniques known for fiber-reactive dyes.

-   For instance, when applied by exhaust dyeing processes to cellulose     fibers from a long liquor using any of a wide variety of     acid-binding agents with or without neutral salts, such as sodium     chloride or sodium sulfate, they produce dyeings with very good     color yields. Dyeing is performed preferably in an aqueous bath at     temperatures between 40 and 105° C., where appropriate at a     temperature up to 130° C. under pressure, and where appropriate in     the presence of customary dyeing assistants. One possible procedure     in this context is to introduce the material into the warm bath and     to heat the bath gradually to the desired dyeing temperature, and to     complete the dyeing operation at that temperature. The neutral salts     which hasten the exhaustion of the dyes may also, where appropriate,     not be added to the bath until the actual dyeing temperature has     been reached.

The padding process likewise provides excellent color yields and very good color build on cellulose fibers, in which case fixing can be accomplished conventionally by batching at room temperature or elevated temperature, at up to about 60° C., for example, by steaming or using dry heat.

Similarly, the customary printing processes for cellulose fibers, which can be carried out either in one phase, by printing for example with a print paste comprising sodium bicarbonate or another acid-binding agent and by subsequent steaming at 100 to 103° C., or in two phases, by for example printing with a neutral or weakly acidic print color and by subsequent fixation either by passing the printed material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor with subsequent batching or steaming or dry heat treatment of the alkali-overpadded material, produce strong prints having well-defined contours and a clear white ground. The outcome of the prints is largely independent of variations in the fixing conditions.

When fixing by means of dry heat in accordance with the customary thermofix processes use is made of hot air and from 120 to 200° C. Besides the customary steam at 101 to 103° C. it is also possible to use superheated steam and pressurized steam at temperatures of up to 160° C.

The acid-binding agents which bring about the fixation of the dyes on the cellulose fibers include for example water-soluble basic salts of the alkali metals and likewise alkaline earth metals of organic or inorganic acids or compounds which release alkali in the heat. Mention may be made in particular of the alkali metal hydroxides and alkali metal salts of weak to medium-strength organic or inorganic acids, the preferred alkali metal compounds being the sodium and potassium compounds. Examples of such acid-binding agents include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, waterglass or trisodiumphosphate. The reactive dyes of the general formula (I) according to the invention are notable for high reactivity, good fixability, very good build, and a high level of fastness to light and to light coupled with perspiration. They can therefore be used in accordance with the exhaust dyeing process at low dyeing temperatures and require only short steaming times in pad-steam processes. The degrees of fixation are high, and the unfixed portions are easily washed off, the difference between the degree of exhaustion and the degree of fixation being remarkably small—that is, the soaping losses being very small. They are also particularly suitable for printing, especially on cotton, but also for printing nitrogenous fibers, such as wool or silk or blend fabrics containing wool or silk.

The reactive dyes of the general formula (I) according to the invention have the further feature that, following the dyeing operation, unfixed dye portions on the fiber material are very easily washed off without whites in the same wash being stained by the dye that becomes detached. This brings advantages of the dyeing operation by saving on wash cycles and hence on costs.

The dyeings and prints produced with the reactive dyes of the general formula (I) according to the invention, especially on cellulose fiber materials, possess high color strength and a high fiber-dye bond stability both in the acidic and in the alkaline range, as well as good light fastness and very good wet fastness properties, such as wash, water, seawater, cross-dyeing, and perspiration fastnesses, and also good fastness to dry heat setting, pleating, and crocking.

The examples below serve to illustrate the invention. The parts and percentages are by weight unless noted otherwise. Parts by weight relate to parts by volume as the kilogram relates to the liter.

-   The compounds described by formula in the examples are given in the     form of the free acid. Generally, however, they are prepared and     isolated in the form of their alkali metal salts, such as lithium,     sodium or potassium salts, and are used in the form of their salts     for dyeing. Similarly, the starting compounds and components     specified in free acid form in the following examples, especially     tabular examples, can be used in the synthesis as such or in the     form of their salts, preferably alkali metal salts.

The absorption maxima (λ_(max)) in the visible range reported for the dyes according to the invention were measured on aqueous solutions of their alkali metal salts.

EXAMPLE 1

Synthesis of a Compound of the Formula (VI) (Precursor)

18.8 parts of 2,4-diaminobenzenesulfonic acid are suspended in 150 parts of water and converted to a neutral solution by adding 20% strength sodium hydroxide solution. At 20° C., 14.7 g of formaldehyde bisulfite (Na salt) are added and the mixture is heated to 50° C. It is subsequently stirred for 4 hours at a pH from 5.0 to 5.5. The solution obtained is concentrated by evaporation or reacted further directly.

-   The yellowish residue obtained following evaporative concentration     corresponds to the compound of the formula (VIa)

¹H-NMR (400 MHz, d₆-DMSO): δ (ppm)=3.77 (d, 2 H, ³J=6.6 Hz, CH₂), 5.28 (s, 2 H, NH₂), 5.54 (t, 1 H, ³J=6.6 Hz, NH), 5.82 (dd, 1 H, ³J=8.1 Hz, ⁴J=2.2 Hz, H_(ar)), 5.86 (d, 1 H, ⁴J=2.2 Hz, H_(ar)), 7.08 (d, 1 H, ³J=8.1 Hz, H_(ar)).

Example 2

A suspension of 28.1 g of 4-(2′-sulfatoethylsulfonyl)aniline in 200 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 21 parts of 31% strength hydrochloric acid and the mixture is stirred for 15 minutes thereafter. Then 13.2 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is stirred for 60 minutes more with nitrite in excess. Excess nitrite is then destroyed by adding 10% strength amidosulfuric acid. The suspension of the diazonium salt is then admixed with the solution of the compound of the formula (Via) prepared in Example 1. The pH is then adjusted to 5-6 by adding 15% strength sodium carbonate solution and coupling is completed at 20° C.

-   Evaporative concentration of the solution gives a dye of the formula     (Ie)     which dyes or prints cotton in reddish yellow shades (λ_(max)=445     nm) with good fastness properties.

The dyes of Examples (3) to (17) are obtained analogously by diazotizing amines R-NH₂ as described in Example 2 and coupling the diazonium compounds with the compound (VIa). Ex. R—NH₂ Coupling component Shade λ_(max) (nm) 3)

yellow 416 4)

yellow 422 5)

yellow 406 6)

yellow 428 7)

yellow 446 8)

yellow 412 9)

yellow 409 10)

yellow 407 11)

yellow 404 12)

yellow 408 13)

yellow 405 14)

yellow 436 15)

yellow 438 16)

yellow 429 17)

yellow 430

Example 18

18.8 parts of 2,4-diaminobenzenesulfonic acid are suspended in 150 parts of water and converted to a neutral solution by adding lithium hydroxide solution. This solution is cooled to 10° C. and admixed dropwise over one hour with 17.4 parts of 2,4,6-trifluoropyrimidine, a pH of 5.5 being maintained using 15% strength sodium carbonate solution. When the addition is complete the mixture is warmed to 20-25° C. and stirred for an hour thereafter. It is then filtered and 6.9 parts of sodium nitrite are added.

-   The filtrate is cooled to 10° C. by introduction of ice and is added     dropwise over 30 minutes to 100 parts of ice and 60 parts of     concentrated hydrochloric acid (31%). This mixture is stirred for an     hour and then the excess nitrite is destroyed by adding     amidosulfuric acid. -   The solution of the compound (VIa) described in Example 1 is then     added dropwise to the acid diazotization, after which the pH is     adjusted to 5.0-5.5 by adding 15% strength sodium carbonate     solution. -   The solution obtained is concentrated by evaporation to give a dye     of the formula     which dyes or prints cotton in yellow shades (λ_(max)=406 nm) with     good fastness properties.

The dyes of Examples (19) to (32) are obtained analogously by diazotizing and subsequently coupling the amino compounds R-NH₂ indicated in the table below by the method indicated in Example 18. Ex. R—NH₂ Coupling component Shade λ_(max) (nm) 19)

yellow 417 20)

yellow 416 21)

yellow 418 22)

yellow 417 23)

yellow 421 24)

yellow 418 25)

yellow 415 26)

yellow 412 27)

yellow 415 28)

yellow 414 29)

yellow 412 30)

yellow 412 31)

yellow 415 32)

yellow 414

Example 33

28.1 parts of 4-(2′-sulfatoethylsulfonyl)aniline are dissolved in 250 parts of water by neutralization of solid sodium bicarbonate. 4.2 parts of sodium fluoride are added to the solution, which is subsequently cooled to 0-5° C. by adding ice. Then, over the course of 5 minutes, 13.5 parts of trifluorotriazine are added dropwise, the pH initially falling rapidly and then leveling out at 4.5 to 5.0.

When the addition is complete, stirring is continued for 15 minutes. Subsequently, a neutralized solution of 18.8 parts of 2,4-diaminobenzenesulfonic acid in water is added dropwise and the pH is adjusted to 6.0-6.5. The reaction is completed by heating at from 30 to 35° C. followed by 60 minutes of stirring. The resulting solution is filtered and 6.9 parts of sodium nitrite are added.

-   The solution obtained is cooled to 10° C. by introduction of ice and     added dropwise over 30 minutes to 100 parts of ice and 60 parts of     concentrated hydrochloric acid (31%). This mixture is stirred for 1     hour and then the excess nitrite is destroyed by adding     amidosulfuric acid. -   The solution of the compound (Via) described in Example 1 is then     introduced dropwise to the acid diazotization. -   A pH of from 2.0 to 2.5 is established. After an hour of subsequent     stirring the mixture is adjusted to a pH of 5.5 using sodium     carbonate solution and then is buffered with NaH₂PO₄/Na₂HPO₄. The     resulting solution is concentrated by evaporation. -   This gives a dye of the formula     which dyes or prints cotton in yellow shades (λ_(max)=408 nm) with     good fastness properties.

The dyes of Examples (35) to (47) are obtained analogously by diazotizing and subsequently coupling the amino compounds R-NH₂ indicated in the table below 25 by the method indicated in Example 33. λ_(max) Ex. R—NH₂ Coupling component Shade (nm) 34)

yellow 416 35)

yellow 414 36)

yellow 419 37)

yellow 419 38)

yellow 421 39)

yellow 422 40)

yellow 422 41)

yellow 419 42)

yellow 418 43)

yellow 408 44)

yellow 409 45)

yellow 407 46)

yellow 409 47)

yellow 411

Example 48

A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 25 parts of 31% strength hydrochloric acid and the mixture is stirred for 15 minutes thereafter. Then 16 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is subsequently stirred for 60 minutes with the nitrite in excess.

-   Excess nitrite is then destroyed by adding 10% strength     amidosulfuric acid. The dye solution described in Example 2 is then     added to the diazonium salt suspension, followed by stirring for 15     minutes. The pH is then adjusted to 5.0-5.5 by adding 15% strength     sodium carbonate solution, and coupling is completed. -   The solution obtained is concentrated by evaporation to give a dye     of the formula     which dyes or prints cotton in a dull orange (λ_(max)=428 nm).

The dyes of the general formula

set out in the table below are obtained by reacting the compound prepared as in Example 1 first as described in Example 2 with an amine A₁-NH₂ and then as described in Example 48 with an amine A₂-NH₂. Ex. A₁—NH₂ A₂—NH₂ Shade 49)

dull orange 50)

dull orange 51)

dull orange 52)

dull orange 53)

dull orange 54)

dull orange 55)

dull orange 56)

dull orange 57)

dull orange 58)

dull orange 59)

dull orange 60)

dull orange 61)

dull orange 62)

dull orange 63)

dull orange 64)

dull orange 65)

dull orange 66)

dull orange 67)

dull orange 68)

dull orange 69)

dull orange 70)

dull orange 71)

dull orange 72)

dull orange 73)

dull orange 74)

dull orange 75)

dull orange 76)

dull orange 77)

dull orange 78)

dull orange 79)

dull orange 80)

dull orange 81)

dull orange 82)

dull orange 83)

dull orange 84)

dull orange 85)

dull orange 86)

dull orange 87)

dull orange 88)

dull orange 89)

dull orange 90)

dull orange 91)

dull orange

Example 92

17.3 parts of aniline-4-sulfonic acid are dissolved in 200 parts of water and acidified by adding 21 parts of 31% strength hydrochloric acid. Ice cooling to 10-15° C. is followed by dropwise addition of 13.2 parts of 40% strength sodium nitrite solution. With an excess of nitrite, stirring is conducted for 60 minutes. The excess is then reduced by adding a few drops of 10% strength amidosulfuric acid solution.

-   The solution obtained in accordance with Example 1 is then added to     the diazonium salt suspension, the pH is adjusted to 4-5 by adding     15% strength sodium carbonate solution, and coupling is completed. -   This gives the solution of a dye of the formula

A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 25 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. Then 16 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is subsequently stirred for 60 minutes with an excess of nitrite.

-   Excess nitrite is then destroyed by adding 10% strength     amidosulfuric acid. The lo above dye solution is then added to the     diazonium salt suspension and the mixture is stirred for 15 minutes.     The pH is then adjusted to 5.0-5.5 by adding 15% strength sodium     carbonate solution, and coupling is completed. -   The solution obtained is concentrated by evaporation to give a dye     of the formula     which dyes or prints cotton in yellowish brown shades (λ_(max)=431     nm).

Examples 93 to 135

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 92 by diazotizing a reactive amine A₁-NH₂ in accordance with Examples 49 to 91 instead of 4-(2′-sulfatoethylsulfonyl)aniline and carrying out coupling in the second stage.

Example 136

19.1 parts of aniline-4-sulfonic acid are dissolved in 220 parts of water and acidified by adding 23 parts of 31% strength hydrochloric acid. Ice cooling to 10-15° C. is followed by dropwise addition of 14.5 parts of 40% strength sodium nitrite solution. With an excess of nitrite, stirring is conducted for 60 minutes. The excess is then reduced by adding a few drops of 10% strength amidosulfuric acid solution.

-   The dye solution described in Example 2 is then added to the     diazonium salt suspension, the pH is adjusted to 4-5 by adding 15%     strength sodium carbonate solution, and coupling is completed. -   The resulting solution is dried by evaporation to give the dye of     formula     which dyes or prints cotton in orange-brown shades (λ_(max)=435 nm).

Examples 137 to 181

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 136 by using a solution of a dye according to Examples 3 to 47 instead of the dye solution described in Example 2.

Example 182

30.3 parts of 2-naphthylamine-4,8-disulfonic acid are dissolved in 300 parts of water and acidified by adding 21 parts of 31% strength hydrochloric acid. Ice cooling to 10-15° C. is followed by dropwise addition of 13.2 parts of 40% strength sodium nitrite solution. With an excess of nitrite, stirring is conducted for 60 minutes. The excess is then reduced by adding a few drops of 10% strength amidosulfuric acid solution.

-   The solution obtained in accordance with Example 1 is then added to     the diazonium salt suspension, the pH is then adjusted to 4-5 by     adding 15% strength sodium carbonate solution, and coupling is     completed. -   This gives the solution of a dye of the formula

A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 25 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. Then 16 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is subsequently stirred for 60 minutes with an excess of nitrite.

-   Excess nitrite is then destroyed by adding 10% strength     amidosulfuric acid. The above dye solution is then added to the     diazonium salt suspension and the mixture is stirred for 15 minutes.     The pH is then adjusted to 5.0-5.5 by adding 15% strength sodium     carbonate solution, and coupling is completed. The solution obtained     is concentrated by evaporation to give a dye of the formula     which dyes or prints cotton in yellowish brown shades (λ_(max)=439     nm).

Examples 183 to 225

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 182 by diazotizing a reactive amine A₁-NH₂ in accordance with Examples 49 to 91 instead of 4-(2′-sulfatoethylsulfonyl)aniline and carrying out coupling in the second stage.

Example 226

33.3 parts of 2-naphthylamine-4,8-disulfonic acid are dissolved in 350 parts of water and acidified by adding 25 parts of 31% strength hydrochloric acid. Ice cooling to 10-15° C. is followed by dropwise addition of 14.5 parts of 40% strength sodium nitrite solution. With an excess of nitrite, stirring is conducted for 60 minutes. The excess is then reduced by adding a few drops of 10% strength amidosulfuric acid solution.

-   The dye solution described in Example 2 is then added to the     diazonium salt suspension, the pH is adjusted to 4-5 by adding 15%     strength sodium carbonate solution, and coupling is completed. -   The resulting solution is dried by evaporation to give the dye of     formula     which dyes or prints cotton in yellow to orange-brown shades     (λ_(max)=429 nm).

Examples 227 to 271

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 226 by using a solution of a dye according to Examples 3 to 47 instead of the dye solution described in Example 2.

Example 272

A suspension of 61.8 g of 4-(2′-sulfatoethylsulfonyl)aniline in 500 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 50 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. Then 32 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is subsequently stirred for 60 minutes with an excess of nitrite.

-   Excess nitrite is then destroyed by adding 10% strength     amidosulfuric acid. The solution obtained in accordance with Example     1 is then added to the diazonium salt suspension and the mixture is     stirred for 15 minutes. The pH is then adjusted to 5.0-5.5 by adding     15% strength sodium carbonate solution, and coupling is completed. -   The solution obtained is concentrated by evaporation to give a dye     of the formula     which dyes or prints cotton in a dull orange to orange shade     (λ_(max)=428 nm).

Examples 273 to 317

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 272 by diazotizing 2.2 equivalents of a reactive amine A₁-NH₂ in accordance with Examples 49 to 91 instead of 4-(2′-sulfatoethylsulfonyl)aniline and reacting the diazonium compound with one equivalent of the coupler from Example 1. 

1. A dye of the general formula (I)

where m is 1 or 2, n is 0 or 1, q is 0, 1, 2 or 3 and p is 0, 1 or 2, r is 0, 1 or 2, and p+r is 1 or 2 and X₁ is a radical —CH₂CH₂Z or —CH═CH₂, Z being an alkali-eliminable group, M is hydrogen, ammonium, an alkali metal or the equivalent of an alkaline earth metal, X₂ is alkyl, alkoxy, halogen, COOM or SO₃M, L is a direct bond or alkylene, L′ is a direct bond or a group of the formula

X₃ is a heterocyclic reactive group of the general formula (IIa) or (IIb)

or a reactive group of the formula (IIc), (IId) or (IIe)

where X₄ to X₆ independently are hydrogen or halogen, with the proviso that at least one radical X₄ to X₆ is halogen, X₇ is halogen or X₈, and X₈ is a substituent of the general formula (III)

where R₁ is hydrogen, alkyl or aryl, B is alkylene, oxygen-interrupted alkylene, arylene or arylalkylene, and R₂ is a radical SO₃M, SO₂-CH₂CH₂Z or SO₂-CH═CH₂, in which Z is as defined above and the ring labeled A is either absent or present.
 2. A dye as claimed in claim 1, wherein X₂ is C₁-C₄ alkyl, C₁-C₄ alkoxy or SO₃M, M being as defined in claim
 1. 3. A dye as claimed in claim 1, wherein X₃ is a group of the formula

where Hal′ is chloro or bromo, R₁′ is hydrogen, methyl, ethyl or phenyl, B′ is ethylene, propylene or —CH₂CH₂—O—CH₂CH₂- and R₂′ is —SO₂CH₂CH₂OSO₃M or —SO₂CH═CH₂.
 4. The dye as claimed in claim 1, wherein m is
 1. 5. The dye as claimed in claim 1, wherein m is
 2. 6. The dye as claimed in claim 1, corresponding to the general formula (Ia)

where X₁ to X₃, A, L, L′, M, m, r, p and q are as defined in claim
 1. 7. The dye as claimed in claim 1, corresponding to the general formula (Ib)

where X₁ to X₃, A, L, L′, M, r, p and q are as defined in claim
 1. 8. The dye as claimed in claim 1, corresponding to the general formula (Ic)

where M, A, X₂ and q are as defined in claim 1 and V is X₃-NH-L- or X₁-O₂S-L′-, where X₁, X₃, L and L′ are as defined in claim
 1. 9. The dye as claimed in claim 1, corresponding to one of the general formulae (Id) to (Iq)

where in each case M is hydrogen or sodium and X₂′ is hydrogen, methyl, ethyl, methoxy, ethoxy, COOM or SO₃M and U is —SO₂CH₂CH₂OSO₃M, —SO₂CH═CH₂ or —NH-U′, in which M is hydrogen or sodium and U′ is one of the formulae

where Hal′ is chloro or fluoro, R₁′ is hydrogen, methyl, ethyl or phenyl, B′ is ethylene, propylene or —CH₂CH₂—O—CH₂CH₂- and R₂′ is —SO₂CH₂CH₂OSO₃M or —SO₂CH═CH₂.
 10. A process for preparing a dye of the general formula (I) as claimed in claim 1 one or more of claims 1 to 9, which comprises diazotizing an aromatic amine of the general formula (V)

where p, q, r, L, X₁, X₂ and X₃ are as defined in claim 1 and coupling the diazonium compound with a compound of the general formula (VI)


11. (canceled)
 12. A process of dyeing of a hydroxyl- and/or carboxamido-containing material which comprises contacting the material with the dye of the general formula (I) as claimed in claim
 1. 13. A process of dyeing of a hydroxyl- and/or carboxamido-containing material which comprises contacting the material with the dye of the general formula (I) as claimed in claim
 9. 14. The process as claimed in claim 12, wherein the material is a fiber material.
 15. The process as claimed in claim 13, wherein the material is a fiber material. 